Hierarchically ordered crystalline microporous materials with long-range mesoporous order having cubic symmetry

ABSTRACT

A composition of matter is provided comprising hierarchically ordered crystalline microporous material having well-defined long-range mesoporous ordering of cubic symmetry. The composition possesses mesopores having walls of crystalline microporous material and a mass of mesostructure between mesopores of crystalline microporous material. Long-range ordering is defined by presence of secondary peaks in an X-ray diffraction (XRD) pattern and/or cubic symmetry observable by microscopy.

FIELD OF THE DISCLOSURE

The present disclosure relates to hierarchically ordered crystallinemicroporous materials.

BACKGROUND OF THE DISCLOSURE

Zeolites are microporous aluminosilicate materials possessingwell-defined structures and uniform pore sizes that can be measured innanometers or angstroms (Å) (pores typically up to about 20 Å).Typically, zeolites comprise framework atoms such as silicon, aluminumand oxygen arranged as silica and alumina tetrahedra. Zeolites aregenerally hydrated aluminum silicates that can be made or selected witha controlled porosity and other characteristics, and typically containcations, water and/or other molecules located in the porous network.Hundreds of natural and synthetic zeolite framework types exist with awide range of applications. Numerous zeolites occur naturally and areextensively mined, whereas a wealth of interdependent research hasresulted in an abundance of synthetic zeolites of different structuresand compositions. The unique properties of zeolites and the ability totailor zeolites for specific applications has resulted in the extensiveuse of zeolites in industry as catalysts (e.g., catalytic cracking ofhydrocarbons or as components in catalytic convertors), molecularsieves, adsorbents (e.g., drying agents), ion exchange materials (e.g.,water softening) and for the separation of gases. Certain types ofzeolites find application in various processes in petroleum refineriesand many other applications. The zeolite pores can form sites forcatalytic reactions, and can also form channels that are selective forthe passage of certain compounds and/or isomers to the exclusion ofothers. Zeolites can also possess an acidity level that enhances itsefficacy as a catalytic material or adsorbent, alone or with theaddition of active components. Described below is only one of thehundreds of types of zeolites that are identified by the InternationalZeolite Association (IZA). Properties and uses of many of these are wellknown.

Zeolite Y (also known as Na-Y zeolite or Y-type faujasite zeolite) is awell-known material for its zeolites have ion-exchange, catalytic andadsorptive properties. Zeolite Y is also a useful starting material forproduction of other zeolites such as ultra-stable y-type zeolite (USY)Like typical zeolites, faujasite is synthesized from alumina and silicasources, dissolved in a basic aqueous solution and crystallized. Thefaujasite zeolite has a framework designated as FAU by the IZA, and areformed by 12-ring structures having made of supercages with pore openingdiameters of about 7.4 angstroms (Å) and sodalite cages with poreopening diameters of about 2.3 Å. Faujasite zeolites are characterizedby a 3-dimensional pore structure with pores running perpendicular toeach other in the x, y, and z planes. Secondary building units can bepositioned at 4, 6, 6-2, 4-2, 1-4-4 or 6-6. An example silica-to-aluminaratio (SAR) range for faujasite zeolite is about 2 to about 6, typicallywith a unit cell size (units a, b and c) in the range of about 24.25 to24.85 Å. Faujasite zeolites are typically considered X-type when the SARis at about 2-3, and Y-type when the SAR is greater than about 3, forinstance about 3-6. Typically, faujasite is in sodium form and can beion exchanged with ammonium, and an ammonium form can be calcined totransform the zeolite to its proton form.

Whereas zeolites have found great utility in their ability to selectbetween small molecules and different cations, mesoporous solids (poresbetween about 20 and 500 Å) offer possibilities for applications forspecies up to an order of magnitude larger in dimensions such asnanoparticles and enzymes. The comparatively bulky nature of suchspecies hinders diffusion through the microporous zeolite network, andthus, a larger porous system is required to effectively perform ananalogous molecular sieving action for the larger species.

Mesoporous silicas are amorphous; however, it is the pores that possesslong-range order with a periodically aligned pore structure and uniformpore sizes on the mesoscale. Mesoporous silicas offer high surface areasand can be used as host materials to introduce additional functionalityfor a diverse range of applications such as adsorption, separation,catalysis, drug delivery and energy conversion and storage.

An attractive property of ordered structures is that their architecturemay be described in relation to their symmetry. The regular form ofcrystals is associated with the regular arrangements of the sub-unitscomprising the crystal, and hence, the symmetry of the crystal isconnected to the symmetry of the sub-units. For example, seven distinctthree-dimensional crystal units are provided in Table 1. The crystalsystems can be sub-divided upon the symmetry elements present,collectively referred to as the point group and provided in Table 2. Forexample, 3m infers that a mirror plane having a three-fold axis ispresent. For the class 3/m (or 6) the mirror plane is perpendicular tothe three-fold axis. In 2D space, such as a lamellar system, havingfewer dimensions than 3D, there are four crystal systems: hexagonal,square, rectangular and oblique.

The well-defined microporous structure of zeolites provides an amalgamof important physicochemical functionalities that are highly desirablein various industrial practices. Their molecular-sized pore channelsembedded with tunable acid/base sites can geometrically discriminate theingress of guest species and direct shape-selective transformations.Such remarkable properties uniquely exhibited by zeolites demonstrateunprecedented importance in numerous chemical technologies, includingbut not limited to oil-refining, detergents and effluent abatement, thatprofoundly impact the global economy and environment. However, zeoliteperformance is often hindered as a result of their poor mass-transferabilities induced by configurational diffusion inside the narrowmicropores. Therefore, mitigation of the intrinsic mass-transferlimitations is important to explore the full potential of zeolites indiverse energy economies and thereby enhance the accessibility tointernal functional sites. Other drawbacks of microporous zeolites ascatalysts in certain reactions are their susceptibility to coking, whichcan lead to accelerated deactivation of catalysts and productselectivity.

In this regard, hierarchically ordered zeolites (HOZs) possessing anordered mesoporous structure and zeolitized mesopore walls are of greattechnological importance due to their exceptional properties. HOZscontain different layers of porosity, that is, mesopores and micropores.Hierarchically ordered zeolites offer advantages over traditionalmicroporous zeolites by, for example, improving diffusion of guestspecies to the active sites, overcoming steric limitations, improvingproduct selectivity, decreasing coke formation, improving hydrothermalstability, and improving accessibility of Brønsted acid sites and Lewisacid sites; and concomitantly, improved catalytic performance.

Numerous synthetic strategies to produce hierarchical zeolites areknown, and fall under two general categories: bottom-up approaches whichinclude the use of hard templates and soft templates, and top-downapproaches which typically involve post-synthetic treatment. Bottom-upstrategies generally involve templating techniques used in situ duringzeolite crystallization, for example using hard templates (carbonsources) or soft templates (surfactants). Top-down strategies generallyinvolve post-synthetic modifications of already formed zeolite crystals,for example, by steaming, dealumination (using an acid) or desilication(using a base). Weaknesses of known processes to produce hierarchicallyordered zeolites is that the long-rage ordering of the mesophase in theresulting zeolite is limited or non-existent, and mesopores can berandom in size, location and ordering.

Base-mediated desilication offers a direct route to creatingmesoporosity in high-silica frameworks obtained from steaming. (see,e.g.: Verboekend, D., Milina, M., Mitchell, S. & Perez-Ramirez, J.Hierarchical Zeolites by Desilication: Occurrence and Catalytic Impactof Recrystallization and Restructuring. Crys. Growth Des. 13,5025-5035(2013)). In particular, integrating organic templates duringthe desilication process has significantly improved crystallinity andmesoporosity. (see, e.g.: García-Martínez, J., Johnson, M., Valla, J.,Li, K. & Ying, J. Y. Mesostructured Zeolite Y—High HydrothermalStability and Superior FCC Catalytic Performance. Catal. Sci. Tech. 2,987 (2012); Mendoza-Castro, M. J., Serrano, E., Linares, N. &García-Martínez, J. Surfactant-Templated Zeolites: From Thermodynamicsto Direct Observation. Adv. Mater. Interfaces 8, 2001388 (2020)).However, such post-synthetic modification strategies typically lackcontrol over the dissolution and self-assembly process, resulting inpoorly interconnected mesopores. (see, e.g.: Schwieger, W. et al.Hierarchy Concepts: Classification and Preparation Strategies forZeolite Containing Materials with Hierarchical Porosity. Chem. Soc. Rev.45, 3353-3376, doi:10.1039/c5cs00599j (2016)).

In view of the prior attempts to produce hierarchically orderedzeolites, there remains a need in the art for hierarchically orderedzeolites. It is in regard to these and other problems in the art thatthe present disclosure is directed to provide a technical solution forcompositions of hierarchically ordered zeolites having well-definedlong-range mesoporous ordering having cubic symmetry.

SUMMARY OF THE DISCLOSURE

A composition of matter is provided comprising crystalline microporousmaterial such as zeolites or zeolite-type materials that arehierarchically ordered. These hierarchically ordered crystallinemicroporous materials have well-defined long-range mesoporous orderingof cubic symmetry comprising mesopores having walls of crystallinemicroporous material and a mass of mesostructure between mesoporescomposed of the crystalline microporous material. Long-range ordering isdefined by presence of secondary peaks in an X-ray diffraction (XRD)pattern and/or cubic symmetry observable by microscopy.

In certain embodiments, a composition of matter comprises hierarchicallyordered crystalline microporous material having well-defined long-rangemesoporous ordering of cubic symmetry comprising mesopores having wallscomposed of crystalline microporous material and a mass of mesostructurebetween mesopores of crystalline microporous material. At least aportion of the mesopores contain micelles of supramolecular templatesshaped to induce mesoporous ordering of cubic symmetry. Thesupramolecular templates possess one or more dimensions larger thandimensions of micropores of the crystalline microporous material toconstrain diffusion into micropores of the crystalline microporousmaterial, wherein the dimensions relate to a head group of asupramolecular template, a tail group of a supramolecular template, or aco-template arrangement that constrain diffusion into micropores of thecrystalline microporous material. In certain embodiments, an ionicco-solute is present in the hierarchically ordered crystallinemicroporous material; in certain embodiments, an ionic co-solutecomprises NO₃ ⁻.

In certain embodiments, the cubic mesophase possess Ia-3d, Fm-3m, Pm-3n,Pn-3m or Im-3m symmetry. In certain embodiments, the cubic mesophasepossess Ia-3d symmetry and secondary peaks in XRD are present at one ormore of (220), (321), (400), (420) or (332) reflections. In certainembodiments, the cubic mesophase possess Ia-3d symmetry and long-rangeordering is observable by microscopy viewing an electron beam down a[311], or zone axis. In certain embodiments, the cubic mesophase possessFm-3m symmetry and long-range ordering is observable by microscopyviewing an electron beam down a or zone axis.

In certain embodiments, the said parent crystalline microporous materialcomprises a zeolite or zeolite-type material. For example, the parentcrystalline microporous material is a zeolite having a frameworkselected from the group consisting of AEI, *BEA, CHA, FAU, MFI, MOR,LTL, LTA and MWW. In certain embodiments the parent crystallinemicroporous material is a zeolite having FAU framework.

In certain embodiments, a hydrocracking catalyst is provided comprisingthe hierarchically ordered zeolite described herein, an inorganic oxidecomponent as a binder, and an active metal component. For example, thehierarchically ordered crystalline microporous material comprises about0.1-99, 0.1-90, 0.1-80, 0.1-70, 0.1-50, 0.1-40, 2-99, 2-90, 2-80, 2-70,2-50, 2-40, 20-100, 20-80, 20-70, 20-50, or 20-40 wt % of thehydrocracking catalyst. An inorganic oxide component is selected fromthe group consisting of alumina, silica, titania, silica-alumina,alumina-titania, alumina-zirconia, alumina-boria, phosphorus-alumina,silica-alumina-boria, phosphorus-alumina-boria,phosphorus-alumina-silica, silica-alumina-titania,silica-alumina-zirconia, alumina-zirconia-titania,phosphorous-alumina-zirconia, alumina-zirconia-titania andphosphorus-alumina-titania. In certain embodiments, the inorganic oxidecomponent comprises alumina. In certain embodiments, the zeolitecomprises FAU zeolite. In certain embodiments, the active metalcomponent comprises one or more of Mo, W, Co or Ni (oxides or sulfides).The active metal component comprises one or more metals selected fromthe Periodic Table of the Elements IUPAC Groups 6, 7, 8, 9 or 10.

In certain embodiments, a method for hydrocracking hydrocarbon oil isprovided, comprising hydrocracking hydrocarbon oil with a hydrocrackingcatalyst including the hierarchically ordered zeolite described herein.In certain embodiments, the hydrocarbon oil comprises a recycle streamobtained from hydrocracking of VGO, straight run VGO or pre-treatedstraight run VGO, with selectivity to naphtha and middle distillatestailored as a function of the cubic symmetry mesophase.

Any combinations of the various embodiments and implementationsdisclosed herein can be used. These and other aspects and features canbe appreciated from the following description of certain embodiments andthe accompanying drawings and claims.

BRIEF DESCRIPTION OF THE DRAWINGS

The process of the disclosure will be described in more detail below andwith reference to the attached drawings in which the same number is usedfor the same or similar elements.

FIGS. 1 and 2 are schematic overviews of hierarchical ordering bypost-synthetic ensembles synthesis route described herein.

FIGS. 3A-B depicts low-angle and high-angle XRD patterns, FIG. 4Adepicts N₂ physisorption isotherms, and FIG. 4B depicts NLDFT pore-sizedistributions, of synthesized materials in examples herein, and a parentzeolite.

FIGS. 5A-B are transmission electron microscopy micrographs ofhierarchically ordered zeolite synthesized in an example herein, andFIG. 5C shows unit cell schematic and dimensions for parent zeolite andtheir arrangement to provide long-range mesoporous ordering.

FIG. 6 is a plot of hydrocracking activity (conversion percentage peracid site) and selectivity (naphtha, middle distillates and heavydistillates) of synthesized materials in examples herein, and a parentzeolite.

DETAILED DESCRIPTION OF CERTAIN EMBODIMENTS OF THE DISCLOSURE

A composition of matter is provided comprising crystalline microporousmaterial (“CMM”) that are hierarchically ordered. These hierarchicallyordered crystalline microporous materials (“HOCMM”) have well-definedlong-range mesoporous ordering of cubic symmetry comprising mesoporeshaving walls of crystalline microporous material and a mass ofmesostructure between mesopores of CMM. The long-range ordering isdefined by presence of secondary peaks in an X-ray diffraction (XRD)pattern and/or cubic symmetry observable by microscopy. In certainembodiments, for example prior to calcination of synthesized HOCMMs, atleast a portion of the mesopores contain micelles of supramoleculartemplates shaped to induce mesoporous ordering of cubic symmetry, andwherein the supramolecular templates possess one or more dimensionslarger than dimensions of micropores of the crystalline microporousmaterial to constrain diffusion into micropores of the crystallinemicroporous material. The dimensions relate to a head group of asupramolecular template, a tail group of a supramolecular template, or aco-template arrangement that constrain diffusion into micropores of theCMM. The HOCMMs are synthesized using by base-mediated reassembly, bydissolution of the parent CMM to the level of structural building unitsthat are oligomers of the parent CMM, and minimizing or avoidingamorphization/structural collapse. The CMM dissolution and self-assemblyis comprehensively controlled to produce HOCMMs according to the methodsherein having mesoporous ordering of cubic symmetry, includingembodiments with the use of an ionic co-solute. A method to makecompositions including those disclosed herein are disclosed inco-pending and commonly owned U.S. patent application Ser. No. ______filed on Jul. 5, 2022 [Docket 00501/011094-US0 (SA4523)] entitled“Methods for Synthesis of Hierarchically Ordered Crystalline MicroporousMaterials with Long-Range Mesoporous Order,” which is incorporated byreference herein.

In certain embodiments of reassembly to produce the composition ofmatter herein: the rate and extent of CMM dissolution is controlled byemploying urea as an in situ base, and by mediating hydrothermaltemperature to control urea hydrolysis and fine-tune pH of the solution;extent of dissolution into smaller oligomers is controlled by thesurfactant-CMM interactions during the initial stages of dissolution,whereby influence of the ion-specific interactions, that is, anionicHofmeister effect (AHE) on supramolecular self-assembly directsformation of hierarchically ordered structures with bicontinuous gyroidcubic mesopore symmetry; in certain embodiments the hierarchicallyordered structures possess bicontinuous gyroid cubic Ia-3d mesoporesymmetry.

According to an embodiment of a method to produce the composition ofmatter herein, a parent CMM is formed into an aqueous suspension with analkaline reagent and a supramolecular templating agent. In additionalembodiments, the aqueous suspension includes an ionic co-solute as anadditional anion that is separate from the anion which is paired withthe cation of the supramolecular template. The system is maintainedunder conditions to induce incision of the parent CMM into oligomericunits of the CMM, with only a minor portion of monomeric units, and toinduce hierarchical reassembly of the oligomeric units intomesostructures. System conditions (including temperature and time ofcrystallization), selection and concentration of supramoleculartemplate, and selection and concentration of alkaline reagent aretailored to control incision of the parent CMM into oligomeric units andto control reassembly of those oligomeric units around the shape(s) ofsupramolecular template micelles. Dissolution of parent CMM isencouraged to the extent of oligomer formation while minimizing monomerformation, which is controlled by selection of supramolecular template,alkaline reagent, optional ionic co-solute and hydrothermal conditions(including temperature and time). In certain embodiments, a substantialportion, a significant portion or a major portion of the parent CMM iscleaved into oligomeric units, with any remainder in the form ofmonomeric units or atomic constituents of the CMM. In certainembodiments, dimensions of the oligomeric units correspond approximatelyto the wall thickness of the synthesized mesoporous structure, theHOCMM. In certain embodiments interface curvature(s) of the micelles andoligomeric units under reassembly is tuned to a desired mesostructureand mesoporosity with the aid of optional ionic co-solute and theHofmeister effect.

Under effective crystallization conditions and time, and using effectivetype(s) of supramolecular template and alkaline reagent at effectiverelative concentrations, hierarchical ordering by post-syntheticensembles occurs: the parent CMM is incised into oligomeric CMM unitsthat rearrange around the shaped micelles formed by the supramoleculartemplates. Hierarchically ordered CMMs having well-defined long-rangemesoporous ordering are formed by the supramolecular templating methodusing the surfactant micelles. The mesopore walls are characterized bythe parent CMM. The effective supramolecular templates include thosehaving one or more properties forming a dimension that blocks all, asubstantial portion, a significant portion or a major portion of thesupramolecular template molecules from entering pores, channels and/orcavities of the parent CMM. These methods disclosed herein effectuatebase-mediated incisions of the CMM crystals, in the presence of thesupramolecular template of the type/characteristic disclosed herein,into oligomeric components, with subsequent reorganization aroundwell-defined micelles by supramolecular templating, into hierarchicallyordered structures having a well-defined long-range mesoporous orderingof 3D-cubic symmetry.

The curvature or shape of the micelles results in the final 3D-cubicmesophase symmetry. Formation of the supramolecular template moleculesinto micelles is dependent upon factors such as the supramoleculartemplate type, supramolecular template concentration, presence orabsence of an ionic co-solute, CMM type(s), crystallization temperature,type of alkaline reagent, concentration of alkaline reagent, pH level ofthe system, and/or presence or absence of other reagents. In general, atlow concentrations supramolecular templates exist as discrete entities.At higher concentrations, that is, above a critical micelleconcentration (CMC), micelles are formed. The hydrophobic interactionsin the system including the supramolecular template alters the packingshape of the supramolecular templates into, for example, spherical,prolate or cylindrical micelles, which can thereafter formthermodynamically stable two-dimensional or three-dimensional liquidcrystalline phases of ordered mesostructures (see, for example, FIG. 1.4of Zana, R. (Ed.). (2005). Dynamics of Surfactant Self-Assemblies:Micelles, Microemulsions, Vesicles and Lyotropic Phases (1st ed.). CRCPress, Chapter 1, which shows self-assembly based on surfactant andsurfactant packing parameter).

In certain embodiments, the Hofmeister series (HS), ion specific effect,or lyotropic sequence is followed for selection of supramoleculartemplates and/or ionic co-solute to control curvature or shape (e.g.,spherical, ellipsoid, cylindrical, or unilamellar structures) of themicelles (see, for example, Beibei Kang, Huicheng Tang, Zengdian Zhao,and Shasha Song. “Hofmeister Series: Insights of Ion Specificity fromAmphiphilic Assembly and Interface Property” ACS Omega 5 (2020):6229-6239). In embodiments of the methods for synthesis ofhierarchically ordered microporous crystalline materials havingwell-defined long-range mesoporous ordering disclosed herein, mesophasetransitions of hierarchical ensembles yield distinct mesostructuresbased on the anionic Hofmeister effect and supramolecular self-assembly.Anions of different sizes and charges possess differentpolarizabilities, charge densities and hydration energies in aqueoussolutions. When paired with a positive supramolecular template headgroup, these properties can affect the short-range electrostaticrepulsions among the head groups and hydration at the micellarinterface, thus changing the area of the head group (a₀). Suchion-specific interactions can be a driving force in changing themicellar curvature and inducing mesophase transition. Based on the HS(SO₄ ²⁻>HPO₄ ²⁻>OAc⁻>Cl⁻>Br⁻>NO₃ ⁻>ClO₄ ⁻>SCN⁻), strongly hydrated ions(left side of the HS) can increase the micellar curvature, whereasweakly hydrated ions can decrease the micellar curvature. A surfactantpacking parameter, g=V/a₀l (V=total volume of surfactant tails, a₀=areaof the head group, l=length of surfactant tail), can be used to describethese mesophase transitions. In embodiments herein, the hierarchicallyordered structures having a well-defined long-range mesoporous orderingof 3D-cubic symmetry are formed by selecting a supramolecular templateand an ionic co-solute.

In the methods for synthesis of hierarchically ordered CMMs havingwell-defined long-range mesoporous ordering disclosed herein, suitablealkaline reagents include one or more basic compounds to maintain thesystem at a pH level of greater than about 8. In certain embodiments thealkaline reagent is provided at a concentration in the aqueoussuspension of about 0.1-2.0 M. In certain embodiments the alkalinereagent is provided at a concentration in the aqueous suspension ofabout 0.1-5 wt %. In certain embodiments the alkaline reagent comprisesurea. In certain embodiments the alkaline reagent comprises ammonia. Incertain embodiments the alkaline reagent comprises ammonium hydroxide.In certain embodiments the alkaline reagent comprises sodium hydroxide.In certain embodiments the alkaline reagent comprises alkali metalhydroxides including hydroxides of sodium, lithium, potassium, rubidium,or cesium.

In certain embodiments the alkaline reagent is effective to enablecontrolled hydrolysis; for example, urea can be used as an alkalineagent, and during hydrolysis urea reacts to form ammonium hydroxide. Insuch embodiments, pH is increased relatively slowly to a maximum pH as afunction of time, which is beneficial to the process, rather than addingan amount of another alkaline reagent such as ammonium hydroxide in theinitial solution to the maximum pH.

In certain embodiments the alkaline reagent comprises alkylammoniumcations, having the general formula R_(X)H_(4-X)N⁺[A⁻], wherein at X=1-4and R₁, R₂, R₃ and R₄ can be the same or different C1-C30 alkyl groups,and wherein [A⁻] is a counter anion can be OH⁻, Br⁻, Cl⁻ or I⁻. Incertain embodiments the alkaline reagent comprises quaternary ammoniumcations with alkoxysilyl groups, phosphonium groups, an alkyl group witha bulkier substituent or an alkoxyl group with a bulkier substituent. Incertain embodiments the alkylammonium cations used in this regardfunction as a base rather than as a surfactant or template.

In certain embodiments using ammonia, ammonium hydroxide or alkali metalhydroxides, amorphous material is also present with the crystallinematerial in the product. In certain embodiments, upon calcining theas-made HOCMMs there is a reduction in the amount of apparent amorphousmaterial present (for example an overall broad band at 25° (2θ) in XRD),indicative of apparent “self-healing” after calcination. In certainembodiments, by the controlled hydrolysis of urea to ammonium hydroxidethere is a reduction in the amount of apparent amorphous materialpresent in the HOCMMs (for example an overall broad band at 25° (2θ) inXRD), when compared with alternative routes such as NaOH or directlywith ammonium hydroxide.

In the methods for synthesis of hierarchically ordered CMMs havingwell-defined long-range mesoporous ordering disclosed herein, suitablesurfactants as supramolecular templates are provided to assist thereassembly and recrystallization of dissolved components (oligomers) bycovalent and/or electrovalent interactions. Supramolecular templates areprovided at a concentration in the aqueous suspension of about 0.01-0.5M. In certain embodiments suitable supramolecular templates are providedat a concentration in the aqueous suspension of about 0.5-10 wt %.Suitable supramolecular templates are characterized by constraineddiffusion within the micropore channels of parent CMM, referred to asbulky surfactants or bulky supramolecular templates. Diffusion ofsupramolecular template molecules into micropore-channels or cavitiesencourages CMM dissolution. This is minimized in the top-down methodsfor synthesis of hierarchically ordered CMMs having well-definedlong-range mesoporous ordering disclosed herein, wherein effectivesupramolecular templates minimize diffusion or partial diffusion thereofinto CMM pore-channels, cavities or window openings. Such supramoleculartemplates possess suitable dimensions to block such diffusion. Thesuitable dimensions can be a based on dimensions of a head group and/ora tail group of a supramolecular template. In certain embodimentssuitable dimensions can be based on a co-template having one or morecomponents with suitable head and/or tail groups, or being a templatesystem arranged in such a way, so as to minimize or block diffusion into CMM pore-channels, cavities or window openings. By minimizingdiffusion of templates into the CMM pore channels, CMM dissolution intooligomers and comprehensive reorganization and assembly into thehierarchically ordered CMMs having well-defined long-range mesoporousordering disclosed herein is encouraged. In certain embodiments, asupramolecular template is one in which at least a substantial portion,a significant portion or a major portion of the surfactant does notenter into pores and/or channels of the CMM. For example, organosilanes(˜0.7 nm) are relatively large compared to quaternary ammoniumsurfactants without such bulky groups including cetyltrimethylammoniumbromide (CTAB) (˜0.25 nm). In certain embodiments, a supramoleculartemplate contains a long chain linear group (>˜0.6 nm). In certainembodiments, a supramolecular template contains an aromatic or aromaticderivative group (>˜0.6 nm). In certain embodiments, supramoleculartemplates contain one or more bulky groups having a dimension based onmodeling of molecular dimensions as a cuboid having dimensions A, B andC, using Van der Waals radii for individual atoms, wherein one or more,two or more, or all three of the dimensions A, B and C are sufficientlyclose in dimension, or sufficiently larger in dimension, that constrainsdiffusion into the micropores of the selected parent CMM.

In certain embodiments an effective surfactant as a supramoleculartemplate contains at least one moiety, as a head group or a tail group,selected from the group consisting of organosilanes, hydroxysilyls,alkoxysilyls, aromatics, branched alkyls, sulfonates, carboxylates,phosphates and combinations comprising one of the foregoing moieties. Incertain embodiments an effective supramolecular template is anorganosilane that contains at least one hydroxysilyl as a head groupmoiety. In certain embodiments an effective supramolecular template isan organosilane that contains at least one hydroxysilyl as a tail groupmoiety. In certain embodiments an effective supramolecular template isan organosilane that contains at least one alkoxysilyl as a head groupmoiety. In certain embodiments an effective supramolecular template isan organosilane that contains at least one alkoxysilyl as a tail groupmoiety. In certain embodiments an effective supramolecular templatecontains at least one aromatic as a head group moiety. In certainembodiments an effective supramolecular template contains at least onearomatic as a tail group moiety. In certain embodiments an effectivesupramolecular template contains at least one branched alkyl as a headgroup moiety. In certain embodiments an effective supramoleculartemplate contains at least one branched alkyl as a tail group moiety. Incertain embodiments an effective supramolecular template contains atleast one sulfonate as a head group moiety. In certain embodiments aneffective supramolecular template contains at least one sulfonate as atail group moiety. In certain embodiments an effective supramoleculartemplate contains at least one carboxylate as a head group moiety. Incertain embodiments an effective supramolecular template contains atleast one carboxylate as a tail group moiety. In certain embodiments aneffective supramolecular template contains at least one phosphate as ahead group moiety. In certain embodiments an effective supramoleculartemplate contains at least one phosphate as a tail group moiety. Thesemoieties are characterized by one or more dimensions that constraindiffusion into pores of a parent CMM. In certain embodiments, in whichthe CMM is characterized by pores of various dimensions, the selectedmoieties are characterized by one or more dimensions that constraindiffusion into the largest pores the parent CMM.

In certain embodiments an effective supramolecular template contains atleast one cationic moiety. In certain embodiments an effectivesupramolecular template contains at least one cationic moiety selectedfrom the group consisting of a quaternary ammonium moiety and aphosphonium moiety. In certain embodiments an effective supramoleculartemplate contains at least one quaternary ammonium group having aterminal alkyl group with 6-24 carbon atoms. In certain embodiments aneffective supramolecular template contains two quaternary ammoniumgroups wherein an alkyl group bridging the quaternary ammonium groupscontains 1-10 carbon atoms. In certain embodiments an effectivesupramolecular template contains at least one quaternary ammonium group,and at least one constituent group, a head group moiety as describedabove. In certain embodiments an effective supramolecular templatecontains at least one quaternary ammonium group, and at least oneconstituent group, a tail group moiety as described above. In certainembodiments an effective supramolecular template contains at least onequaternary ammonium group, at least one constituent group, a head groupmoiety as described above, and an alkyl group that contains 1-10 carbonatoms bridging at least one of the quaternary ammonium groups and atleast one of the head groups. In certain embodiments an effectivesupramolecular template contains at least one quaternary ammonium group,at least one constituent group, a tail group moiety as described above,and an alkyl group that contains 1-10 carbon atoms bridging at least oneof the quaternary ammonium groups and at least one of the tail groups.

In certain embodiments an effective supramolecular template comprises aquaternary ammonium compound and a constituent group comprising one ormore bulky organosilane or alkoxysilyl substituents. In certainembodiments an effective supramolecular template comprises a quaternaryammonium compound and a constituent group comprising one or morelong-chain organosilane or alkoxysilyl substituents. In certainembodiments an effective supramolecular template cation comprisesdimethyloctadecyl(3-trimethoxysilyl-propyl)-ammonium or derivatives ofdimethyloctadecyl(3-trimethoxysilyl-propyl)-ammonium. In certainembodiments an effective supramolecular template cation comprisesdimethylhexadecyl(3-trimethoxysilyl-propyl)-ammonium or derivatives ofdimethylhexadecyl(3-trimethoxysilyl-propyl)-ammonium. In certainembodiments an effective supramolecular template cation comprises adouble-acyloxy amphiphilic organosilane such as[2,3-bis(dodecanoyloxy)-propyl](3-(trimethoxy silyl)propyl)-dimethylammonium or derivatives of[2,3-bis(dodecanoyloxy)-propyl](3-(trimethoxysilyl)propyl)-dimethylammonium.

In certain embodiments an effective supramolecular template comprises aquaternary phosphonium compound and a constituent group comprising oneor more bulky aromatic substituents. In certain embodiments an effectivesupramolecular template comprises a quaternary phosphonium compound anda constituent group comprising one or more bulky alkoxysilyl ororganosilane substituents.

In certain embodiments an effective supramolecular template contains atail group moiety selected from the group consisting of aromatic groupscontaining 6-50, 6-25, 10-50 or 10-25 carbon atoms, alkyl groupscontaining 1-50, 1-25, 5-50, 5-25, 10-50 or 10-25 carbon atoms, arylgroups containing 1-50, 1-25, 5-50, 5-25, 10-50 or 10-25 carbon atoms,or a combination of aromatic and alkyl groups having up to 50 carbonatoms. In certain embodiments an effective supramolecular templatecontains a head group moiety selected from the group consisting ofaromatic groups containing 6-50, 6-25, 10-50 or 10-25 carbon atoms,alkyl groups containing 1-50, 1-25, 5-50, 5-25, 10-50 or 10-25 carbonatoms, aryl groups containing 1-50, 1-25, 5-50, 5-25, 10-50 or 10-25carbon atoms, or a combination of aromatic and alkyl groups having up to50 carbon atoms. In certain embodiments an effective supramoleculartemplate contains co-templated agents selected from the group consistingof quaternary ammonium compounds (including for example quaternary alkylammonium cationic species) and quaternary phosphonium compounds.

In certain embodiments effective supramolecular templates comprise (a)at least one of: aromatic quaternary ammonium compounds, branched alkylchain quaternary ammonium compounds, alkyl benzene sulfonates, alkylbenzene phosphonates, alkyl benzene carboxylates, or substitutedphosphonium cations; and (b1) and a constituent group comprising atleast one of organosilanes, hydroxysilyls, alkoxysilyls, aromatics,branched alkyls, sulfonates, carboxylates or phosphates, as a headgroup; or (b2) and a constituent group comprising at least one oforganosilanes, hydroxysilyls, alkoxysilyls, aromatics, branched alkyls,sulfonates, carboxylates or phosphates, as a tail group. In certainembodiments effective supramolecular templates include a sulfonate group(a non-limiting example is sulfonatedbis(2-hydroxy-5-dodecylphenyl)methane (SBHDM)). In certain embodimentseffective supramolecular templates include a carboxylate group (anon-limiting example is sodium 4-(octyloxy) benzoate). In certainembodiments effective supramolecular templates include a phosphonategroup (a non-limiting example is tetradecyl(1,4-benzene)bisphosphonate).In certain embodiments effective supramolecular templates include anaromatic group (a non-limiting example is benzylcetyldimethylammoniumchloride). In certain embodiments effective supramolecular templatesinclude an aliphatic group (a non-limiting example is tetraoctylammoniumchloride).

The supramolecular template is provided as a cation/anion pair. Incertain embodiments a cation of a supramolecular template is asdescribed above is paired with an anion selected such as Cl⁻, Br⁻, OH⁻,F⁻ and I⁻. In certain embodiments a cation of a supramolecular templateis as described above is paired with an anion such as Cl⁻, Br⁻ or OH⁻.In certain embodiments an effective supramolecular template comprisesdimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride (commonlyabbreviated as “TPOAC”) or derivatives ofdimethyloctadecyl[3-(trimethoxysilyl)propyl] ammonium chloride. Incertain embodiments an effective supramolecular template comprisesdimethylhexadecyl[3-(trimethoxysilyl)propyl] ammonium chloride orderivatives of dimethylhexadecyl[3-(trimethoxysilyl)propyl] ammoniumchloride. In certain embodiments an effective supramolecular templatecomprises[2,3-bis(dodecanoyloxy)-propyl](3-(trimethoxysilyl)propyl)-dimethylammoniumiodide or derivatives of[2,3-bis(dodecanoyloxy)-propyl](3-(trimethoxysilyl)propyl)-dimethylammoniumiodide.

In certain embodiments, the system includes an effective amount of anionic co-solute (that is, in addition to the anion paired with thesupramolecular template). In certain embodiments in which an ionicco-solute is used it is provided at a concentration in the aqueoussuspension of about 0.01-0.5 M. In certain embodiments in which an ionicco-solute is used it is provided at a concentration in the aqueoussuspension of about 0.01-5 wt %. In certain embodiments an ionicco-solute is selected from the group consisting of CO₃ ²⁻, SO₄ ²⁻, S₂O₃²⁻, H₂PO₄ ⁻, F⁻, Cl⁻, Br⁻, NO₃ ⁻, I⁻, ClO₄ ⁻, SCN⁻ and C₆H₅O₈ ⁻³(citrate). In certain embodiment an ionic co-solute is selected based onthe Hofmeister series/Lyotropic series to control the curvature/shape ofthe micelles to yield the desired cubic mesophase symmetry. In certainembodiments a nitrate (NO₃ ⁻) is an ionic co-solute selected based onthe Hofmeister series/Lyotropic series to control the curvature/shape ofthe micelles to yield hierarchically ordered CMMs having well-definedlong-range mesoporous ordering possess a cubic mesophase symmetry; incertain embodiments using nitrate as an ionic co-solute, a nitrate saltis used, such as ammonium nitrate or a metal nitrate, wherein the metalcan be an alkali metal, an alkali earth metal, a transition metal, anoble metal or a rare earth metal.

The present disclosure is applicable to various types of CMMs as aparent material, including zeolite or zeolite-type materials. In certainembodiments a parent CMM exhibits both good crystallinity andAl-distribution to obtain high-quality HOCMMs while minimizing compositephases and/or impurities.

Suitable zeolitic materials as a parent CMM include those identified bythe International Zeolite Association, including those with theidentifiers ABW, ACO, AEI, AEL, AEN, AET, AFG, AFI, AFN, AFO, AFR, AFS,AFT, AFV, AFX, AFY, AHT, ANA, ANO, APC, APD, AST, ASV, ATN, ATO, ATS,ATT, ATV, AVE, AVL, AWO, AWW, BCT, BEC, BIK, BOF, BOG, BOZ, BPH, BRE,BSV, CAN, CAS, CDO, CFI, CGF, CGS, CHA, -CHI, -CLO, CON, CSV, CZP, DAC,DDR, DFO, DFT, DOH, DON, EAB, EDI, EEI, EMT, EON, EPI, ERI, ESV, ETL,ETR, ETV, EUO, EWO, EWS, EZT, FAR, FAU, FER, FRA, GIS, GIU, GME, GON,GOO, HEU, IFO, IFR, -IFT, -IFU, IFW, IFY, IHW, IMF, IRN, IRR, -IRY, ISV,ITE, ITG, ITH, ITR, ITT, -ITV, ITW, IWR, IWS, IWV, IWW, JBW, JNT, JOZ,JRY, JSN, JSR, JST, JSW, KFI, LAU, LEV, LIO, -LIT, LOS, LOV, LTA, LTF,LTJ, LTL, LTN, MAR, MAZ, MEI, MEL, MEP, MER, MFI, MFS, MON, MOR, MOZ,MRT, MSE, MSO, MTF, MTN, MTT, MTW, MVY, MWF, MWW, NAB, NAT, NES, NON,NPO, NPT, NSI, OBW, OFF, OKO, OSI, OSO, OWE, -PAR, PAU, PCR, PHI, PON,POR, POS, PSI, PTO, PTT, PTY, PUN, PWN, PWO, PWW, RHO, -RON, RRO, RSN,RTE, RTH, RUT, RWR, RWY, SAF, SAO, SAS, SAT, SAV, SBE, SBN, SBS, SBT,SEW, SFE, SFF, SFG, SFH, SFN, SFO, SFS, SFW, SGT, SIV, SOD, SOF, SOR,SOS, SOV, SSF, SSY, STF, STI, STT, STW, -SVR, SVV, SWY, -SYT, SZR, TER,THO, TOL, TON, TSC, TUN, UEI, UFI, UOS, UOV, UOZ, USI, UTL, UWY, VET,VFI, VNI, VSV, WEI, -WEN, YFI, YUG, ZON, *BEA, *CTH, *-EWT, *-ITN, *MRE,*PCS, *SFV, *-SSO, *STO, *-SVY and *UOE. For example, certain zeolitesknown to be useful in the petroleum refining industry include but arenot limited to AEI, *BEA, CHA, FAU, MFI, MOR, LTL, LTA or MWW. Incertain embodiments a parent zeolite can be (FAU) framework zeolite,which includes USY, for example having a micropore size related to the12-member ring when viewed along the [111] direction of 7.4×7.4 Å. Incertain embodiments a parent zeolite can be (MFI) framework zeolite,which includes ZSM-5, for example having a micropore size related to the10-member rings when viewed along the [100] and [010] directions of5.5×5.1 Å and 5.6×5.3 Å, respectively. In certain embodiments a parentzeolite can be (MOR) framework zeolite, which includes mordenitezeolites, for example having a micropore size related to the 12-memberring and 8-member ring when viewed along the [001] and [001] directionsof 6.5×7.0 Å and 2.6×5.7 Å, respectively. In certain embodiments aparent zeolite can be (*BEA) framework zeolite, which includes zeolitebeta polymorph A, for example having a micropore size related to the12-member rings when viewed along the [100] and [001] directions of6.6×6.7 Å and 5.6×5.6 Å, respectively. In certain embodiments a parentzeolite can be (CHA) framework zeolite, which includes chabazitezeolite, for example having a micropore size related to the 8-memberring when viewed normal to the [001] direction of 3.8×3.8 Å. In certainembodiments a parent zeolite can be (LTL) framework zeolite, whichincludes Linde Type L zeolite (zeolite L), for example having amicropore size related to the 12-member ring when viewed along the [001]direction of 7.1×7.1 Å. In certain embodiments a parent zeolite can be(LTA) framework zeolite, which includes Linde Type A zeolite (zeoliteA), for example having a micropore size related to the 8-member ringwhen viewed along the [100] direction of 4.1×4.1 Å. In certainembodiments a parent zeolite can be (AEI) framework zeolite, for examplehaving a micropore size related to the 8-member ring when viewed normalto the [001] direction of 3.8×3.8 Å. In certain embodiments a parentzeolite can be (MWW) framework zeolite, which includes MCM-22, forexample having a micropore size related to the 10-member rings whenviewed normal to [001] direction ‘between layers’ and ‘within layers’ of4.0×5.5 Å and 4.1×5.1 Å, respectively.

In certain embodiments a parent CMM is a zeolite-type material, forexample, aluminophosphates (AlPO), silicon-substituted aluminophosphates(SAPO), or metal-containing aluminophosphates (MAPO). In certainembodiments a parent CMM is a zeolitic siliceous only frameworkmaterial.

As described above, embodiments herein include supramolecular templatesthat contain one or more bulky groups having a dimension based onmodeling of molecular dimensions as a cuboid having dimensions A, B andC, using Van der Waals radii for individual atoms, wherein one or more,two or more, or all three of the dimensions A, B and C are sufficientlyclose in dimension, or sufficiently larger in dimension, that constrainsdiffusion into the micropores of the CMM. Also as described above withrespect to the known parameters related to pore dimensions for exemplaryzeolites, such parameters influence the selection of a supramoleculartemplate. For instance, in the examples herein, FAU zeolite is used;when the supramolecular template material was CTAB (˜0.25 nm), HOCMMswere not realized; however, when the supramolecular template was anorganosilane (˜0.7 nm), HOCMMs were realized, as these are closer indimension to the pore dimensions for FAU zeolite and therefore areconstrained from entering such pores. Likewise, suitable supramoleculartemplates are determined based on a selected parent CMM.

In certain embodiments parent CMMs used in the methods are zeolitesherein having a SAR suitable for the particular type of zeolite. Ingeneral, the SAR of parent zeolites can be in the range of about2-10000, 2-5000, 2-500, 2-100, 2-80, 5-10000, 5-5000, 5-500, 5-100,5-80, 10-10000, 10-5000, 10-500, 10-100, 10-80, 50-10000, 50-5000,50-1000, 50-500 or 50-100. In certain embodiments the SAR of the parentzeolite is greater than or equal to 5 or 10 to achieve long-rangeordering. In embodiments with a SAR of less than 10, uniformmesoporosity and certain degree of ordering is attainable, and amorphousframework material remains in the product.

FIGS. 1 and 2 are schematic overviews of a method to make thecompositions disclosed herein, using a hierarchical ordering bypost-synthetic ensembles synthesis route, including the generalsynthesis mechanism of and how AHE influences g values to alter themicellar curvature and induce mesophase transition. Although the CMMschematically depicted in FIGS. 1 and 2 is FAU zeolite, it isappreciated that other CMMs can be utilized as a parent CMM to form thecompositions herein by post-synthetic ensembles synthesis route.

The method includes base-mediated dissolution/incision of parent CMMsinto oligomeric components, and reorganization into hierarchicallyordered mesostructures by supramolecular templating, and in certainembodiments by the Hofmeister effect. The parent CMM 10 is provided incrystalline form. An effective amount of an alkaline reagent and aneffective amount of a surfactant for supramolecular templating are addedto form an aqueous suspension, and that suspension is maintained underhydrothermal conditions to form oligomeric CMM units 12 of the parentCMM (such as oligomeric zeolitic units when the parent CMM is zeolite).The supramolecular template molecules 14 form into shaped micelles 16and oligomeric CMM units hierarchically reassemble and crystallizearound the shaped micelles as an ordered mesostructure, HOCMM 18, havingmesopores 20 of defined symmetry and mesopore walls formed of theoligomeric CMM units thereby retaining micropores 22 of the underlyingCMM structure of the parent CMM. In certain embodiments, a compositionof matter herein is the HOCMM 18 that contains shaped micelles 16. Incertain embodiments, a composition of matter herein is the HOCMM 18having the surfactant 14 formed into shaped micelles 16 removed, forexample by: chemical methods such as solvent extraction, chemicaloxidation, or ionic liquid treatment; or physical methods such ascalcination, supercritical CO₂, microwave-assisted treatment,ultrasonic-assisted treatment, ozone treatment, or plasma technology.

Referring particularly to FIG. 2 , the general synthesis mechanism isshown including a schematic representation of AHE influence on g valuesand concomitantly the micellar curvature and the induced mesophasetransition. In certain embodiments, a nitrate is used as an ionicco-solute, the micellar curvature is represented by a surfactant packingparameter g in the range of about ½ to about ⅔ and the resulting HOCMMpossesses long-range mesoporous ordering of cubic symmetry. Ion-specificinteractions (The Hofmeister effect) on the micellar curvature in aself-assembly process are apparent. Anions of different sizes andcharges possess different polarizabilities, charge densities andhydration energies in aqueous solutions. When paired with a positivesurfactant head group, these properties can affect the electrostaticrepulsions among the head groups and hydration at the micellarinterface, thus changing the area of the head group (a₀). Suchshort-range ion-specific interactions can be a significant driving forcein changing the micellar curvature and inducing mesophase transition.Based on the Hofmeister series (SO₄ ²⁻>HPO₄ ²⁻>OAc⁻>Cl⁻>Br⁻>NO₃ ⁻>ClO₄⁻>SCN⁻), the strongly hydrated ions (left side of series) can increasethe micellar curvature, whereas weakly hydrated ions can decrease themicellar curvature.

An effective amount of a solvent is used in the process. In certainembodiments the solvent is water. In certain embodiments the solvent iswater in the presence of co-solvents selected from the group consistingof polar solvents, non-polar solvents and pore swelling agents (such as1,3,5-trimethylbenzene). In certain embodiments the solvent selectedfrom the group consisting of polar solvents, non-polar solvents and poreswelling agents (such as 1,3,5-trimethylbenzene), in the absence ofwater. In an embodiment, mixture components are added with water to thereaction vessel prior to heating. Typically, water allows for adequatemixing to realize a more homogeneous distribution of the suspensioncomponents, which ultimately produces a more desirable product becauseeach crystal is more closely matched in properties to the next crystal.Insufficient mixing could result in undesirable products with respect toamorphous phases or a lesser degree of long-range order.

The suspension components are combined in any suitable sequence and aresufficiently mixed to form a homogeneous distribution of the suspensioncomponents. The suspension can be maintained in an autoclave underautogenous pressure (from the components or from the components plus anaddition of a gas purge into the vessel prior to heating), or in anothersuitable vessel, under agitation such as by stirring, tumbling and/orshaking. Mixing of the suspension components is conducted between about20-60, 20-50 or 20-40° C.

The steps of incision and reassembly occur during hydrothermal treatmentto form a solid (product, HOCMM having well-defined long-rangemesoporous ordering of 3D-cubic symmetry) suspended in a supernatant(mother liquor). Hydrothermal treatment is conducted: for a period ofabout 4-168, 12-168, 24-168, 4-96, 12-96 or 24-96 hours; at atemperature of about 70-250, 70-210, 70-180, 70-150, 90-250, 90-210,90-180, 90-150, 110-250, 110-210, 110-180 or 110-150° C.; and at apressure of about atmospheric to autogenous pressure. In certainembodiments hydrothermal treatment occurs in a vessel that is the sameas that used for mixing, or the suspension is transferred to anothervessel (such as another autoclave or low-pressure vessel). In certainembodiments the vessel used for hydrothermal treatment is static. Incertain embodiments the vessel used for hydrothermal treatment is underagitation that is sufficient to suspend the components.

The HOCMM having well-defined long-range mesoporous ordering of 3D-cubicsymmetry is the product recovered. The solids are recovered using knowntechniques such as centrifugation, decanting, gravity, vacuumfiltration, filter press, or rotary drums. The recovered HOCMM havingwell-defined long-range mesoporous ordering of 3D-cubic symmetry isdried, for example at a temperature of about 50-150, 50-120, 80-150 or80-120° C., at atmospheric pressure or under vacuum conditions, for atime of about 0.5-96, 12-96 or 24-96 hours.

In certain embodiments, the dried HOCMM having well-defined long-rangemesoporous ordering of 3D-cubic symmetry is calcined, for example toremove supramolecular templates that remain in the mesopores and otherconstituents from the mesopores and/or the discrete zeolite cellmicropores. The conditions for calcination in embodiments in which it iscarried out can include temperatures in the range of about 350-650,350-600, 350-550, 500-650, 500-600 or 500-550° C., atmospheric pressureor under vacuum, and a time period of about 2.5-24, 2.5-12, 5-24 or 5-12hours. Calcining can occur with ramp rates in the range of from about0.1-10, 0.1-5, 0.1-3, 1-10, 1-5 or 1-3° C. per minute. In certainembodiments calcination can have a first step ramping to a temperatureof between about 100-150° C. with a holding time of from about 1.5-6 or1-12 hours (at ramp rates of from about 0.1-5, 0.1-3, 1-5 or 1-3° C. permin) before increasing to a higher temperature with a final holding timein the range of about 1.5-6 or 1-12 hours.

In certain embodiments, the supernatant remaining after recovery ofproduct from the system is recovered, and all or a portion thereof canbe reused as all or a portion of the solution in a subsequent processfor synthesis of HOCMM having well-defined long-range mesoporousordering of 3D-cubic symmetry, or another HOCMM. In this embodiment,recovered supernatant used in subsequent process is referred to assupernatant from a prior synthesis. In certain embodiments a newsynthesis can occur using supernatant from a prior synthesis togetherwith parent CMM. In certain embodiments a new synthesis can occur usingsupernatant from a prior synthesis together with parent CMM and anadditional quantity of make-up alkaline reagent (for example urea). Incertain embodiments a new synthesis can occur using supernatant from aprior synthesis together with parent CMM and an additional quantity ofmake-up supramolecular template. In certain embodiments a new synthesiscan occur using supernatant from a prior synthesis together with parentCMM and an additional quantity of make-up ionic co-solute. In certainembodiments a new synthesis can occur using supernatant from a priorsynthesis together with parent CMM and an additional quantity of make-upalkaline reagent (for example urea) and/or make-up supramoleculartemplate and/or optional make-up ionic co-solute.

The composition of matter recovered as described herein arehierarchically ordered CMMs (such as zeolites) having well-definedlong-range mesoporous ordering of 3D-cubic symmetry. These arecharacterized by defined mesoporous channel directions with CMMmicropore channels in the walls of the mesostructure. The HOCMM havingwell-defined long-range mesoporous ordering recovered from synthesispossesses supramolecular template as described herein in the mesopores(that is, prior to calcination or extraction of the supramoleculartemplate). In certain embodiments the HOCMM having well-definedlong-range mesoporous ordering of 3D-cubic symmetry recovered fromsynthesis possesses micelles of supramolecular template as describedherein in the mesopores (that is, prior to calcination or extraction ofthe supramolecular template). The composition of matter recovered asdescribed herein retains the structural integrity of the microporouszeolite structure by controlled incision of the parent zeolite followedby controlled reassembly of the zeolite oligomers under a controlledmicellar curvature to yield the HOCMMs with defined mesoporous 3D-cubicsymmetry.

This well-defined long-range mesoporosity is elusive in the field ofhierarchically ordered zeolites. The long-range order is defined bysecondary peaks associated with the periodic arrangement of mesopores inx-ray diffraction (XRD) patterns for the given mesophase, and/or byobservations in microscopy, as demonstrated in the examples herein.These peaks associated with the mesoporous traits of the products areobserved at low 20 angles. The material also exhibits high-angle peaksassociated with the zeolites and are observed at high 2-theta angles. Incertain embodiments the low-angle peaks refer to those occurring at 20angles less than about 6°.

In certain embodiments herein, long-range mesoporous ordering of HOCMMsproduced according to the methods described herein are characterized bythe mesopore periodicity repeating over a length of greater than about50 nm.

In certain embodiments herein, HOCMMs having well-defined long-rangemesoporous ordering of 3D-cubic symmetry herein possess a surface areaof about 200-1500, 200-1000,200-900,400-1500,400-1000,400-900,500-1500,500-1000 or 500-900 m²/g. Inembodiments herein, the HOCMMs having well-defined long-range mesoporousordering of 3D-cubic symmetry herein possess mesoporous pore size ofabout 2-50, 2-20 or 2-10 nm. In embodiments herein, the HOCMMs havingwell-defined long-range mesoporous ordering of 3D-cubic symmetry hereinpossess a silica-to-alumina ratio of about 2.5-1500, 3-1500, 4-1500,5-1500, 6-1500, 2.5-1000, 3-1000, 4-1000, 5-1000, 6-1000, 2.5-500,3-500, 4-500, 5-500, 6-500, 2.5-100, 3-100, 4-100, 5-100, or 6-100. Inembodiments herein, the HOCMMs having well-defined long-range mesoporousordering of 3D-cubic symmetry herein possess a total pore volume ofabout 0.01-1.50, 0.01-1.0, 0.01-0.75, 0.01-0.65, 0.1-1.50, 0.1-1.0,0.1-0.75, 0.1-0.65, 0.2-1.50, 0.2-1.0, 0.2-0.75, 0.2-0.65, 0.3-1.50,0.3-1.0, 0.3-0.75 or 0.3-0.65 cc/g.

In embodiments herein, a product produced by the above method anddemonstrated in an example herein is characterized by a mesophase havingcubic symmetry. In certain embodiments the product is a 3D-cubic orderedmesoporous zeolite. HOCMMs with the mesophase having cubic symmetry arecharacterized by cubic mesoporous channel directions with CMM microporechannels in the walls of the mesostructure. The cubic mesophase canpossess one of Ia-3d, Fm-3m, Pm-3n, Pn-3m or Im-3m symmetry. Inembodiments herein the cubic mesophase possesses Ia-3d symmetry andsecondary XRD peaks associated with the periodic arrangement ofmesopores are present at one or more of the (220), (321), (400), (420)and (332) reflections. In embodiments herein the cubic mesophasepossesses Ia-3d symmetry and the high-degree of long-range cubicmesophase ordering is observable by microscopy viewed by the electronbeam down a suitable zone axis, for example the [311], [111] or [110]zone axes. In the example herein, nitrate salt (NO₃) is used as an ionicco-solute is used to generate the mesophase having cubic symmetry. Inthese embodiments CMM structures are arranged in a cubic symmetry on themeso-scale, where the CMM particles (regardless of their atomic-levelsymmetry or structure) are arranged around micelles (on the meso-scale),and whereby the micelles are arranged exhibiting cubic symmetry.Accordingly, HOCMM having a cubic mesophase includes CMM characterizedby atomic-level symmetry and possessing micropores that are inherent tothat type of CMM, arranged in a cubic symmetry at the meso-scale levelwith mesopores, wherein walls of the mesopores and a mass of themesostructure between mesopores is characterized by said CMM (e.g.,crystalline zeolite). This is created as described herein by formingoligomers of the underlying CMM and arranging those oligomers arrangedaround micelles exhibiting cubic symmetry on the meso-scale. In oneembodiment a HOCMM is provided including MFI zeolite having atomic-levelorthorhombic symmetry arranged in a cubic symmetry meso-scale, whereinduring synthesis of hierarchically ordered zeolite from parent MFIzeolite, oligomers of the parent MFI zeolite are formed and arrangedaround micelles exhibiting cubic symmetry on the meso-scale. In oneembodiment a HOCMM is provided including CHA zeolite having atomic-leveltrigonal symmetry arranged in a cubic symmetry meso-scale, whereinduring synthesis of hierarchically ordered zeolite from parent CHAzeolite, oligomers of the parent CHA zeolite are formed and arrangedaround micelles exhibiting cubic symmetry on the meso-scale. In oneembodiment a HOCMM is provided including BEA zeolite having atomic-leveltetragonal symmetry arranged in a cubic symmetry meso-scale, whereinduring synthesis of hierarchically ordered zeolite from parent BEAzeolite, oligomers of the parent BEA zeolite are formed and arrangedaround micelles exhibiting cubic symmetry on the meso-scale. In oneembodiment a HOCMM is provided including MWW zeolite having atomic-levelhexagonal symmetry arranged in a cubic symmetry meso-scale, whereinduring synthesis of hierarchically ordered zeolite from parent MWWzeolite, oligomers of the parent MWW zeolite are formed and arrangedaround micelles exhibiting cubic symmetry on the meso-scale. In oneembodiment a HOCMM is provided including FAU zeolite having atomic-levelcubic symmetry arranged in a cubic symmetry meso-scale, wherein duringsynthesis of hierarchically ordered zeolite from parent FAU zeolite,oligomers of the parent FAU zeolite are formed and arranged aroundmicelles exhibiting cubic symmetry on the meso-scale.

HOCMMs produced according to the present disclosure are effective ascatalysts, or components of catalysts, in hydrocracking of hydrocarbonoil. In certain embodiments, a method for hydrocracking hydrocarbon oilis provided herein, including hydrocracking hydrocarbon oil with ahydrocracking catalyst including hierarchically ordered zeolite producedaccording to the present disclosure. In certain embodiments, a methodfor hydrocracking hydrocarbon oil is provided herein, includinghydrocracking hydrocarbon oil with a hydrocracking catalyst includinghierarchically ordered FAU zeolite produced according to the presentdisclosure. In certain embodiments, a method for hydrocrackinghydrocarbon oil is provided herein, including hydrocracking hydrocarbonoil with a hydrocracking catalyst including hierarchically orderedcrystalline microporous material having well-defined long-rangemesoporous ordering of cubic symmetry comprising mesopores having wallsof crystalline microporous material and a mass of mesostructure betweenmesopores of crystalline microporous material.

HOCMMs according to the present disclosure are effective as catalysts,or components of catalysts, in hydrocracking of hydrocarbon oil. TheHOCMM can be used as a support having loaded thereon one or more activemetal components as a hydrocracking catalyst. The active metalcomponents are loaded, for example, carried on surfaces including themesopore wall surfaces, micropore wall surfaces or mesopore andmicropore wall surfaces; the active metal components are loadedaccording to known methods, such as providing an aqueous solution of theactive metal components and subjecting HOCMM as catalyst supportmaterial to immersion, incipient wetness, and evaporative, or any othersuitable method. In certain embodiments, the CMM of the HOCMM compriseszeolite. In certain embodiments the CMM of the HOCMM comprises one ormore zeolite types AEI, *BEA, CHA, FAU, MFI, MOR, LTL, LTA or MWW. Incertain embodiments the CMM of the HOCMM comprises FAU zeolite.

The content of the HOCMM and the active metal component areappropriately determined according to the object. In certainembodiments, a hydrocracking catalyst comprises as a support the HOCMMand an inorganic oxide component, typically as a binder and/orgranulating agent. For example, support particles (prior to loading ofone or more hydrocracking active metal components) can contain HOCMM inthe range of about 0.1-99, 0.1-90, 0.1-80, 0.1-70, 0.1-50, 0.1-40, 2-99,2-90, 2-80, 2-70, 2-50, 2-40, 20-100, 20-90, 20-80, 20-70, 20-50, or20-40 wt %, with the remaining content being the inorganic oxide. Incertain embodiments, support particles (prior to loading of one or morehydrocracking active metal components) can contain HOCMM in the range ofabout 0.1-99, 0.1-90, 0.1-80, 0.1-70, 0.1-50, 0.1-40, 2-99, 2-90, 2-80,2-70, 2-50, 2-40, 20-100, 20-90, 20-80, 20-70, 20-50, or 20-40 wt %,with the remaining content being the inorganic oxide and one or moreother zeolitic materials.

As the inorganic oxide component, any material used in hydrocracking orother catalyst compositions in the related art can be used. Examplesthereof include alumina, silica, titania, silica-alumina,alumina-titania, alumina-zirconia, alumina-boria, phosphorus-alumina,silica-alumina-boria, phosphorus-alumina-boria,phosphorus-alumina-silica, silica-alumina-titania,silica-alumina-zirconia, alumina-zirconia-titania,phosphorous-alumina-zirconia, alumina-zirconia-titania andphosphorus-alumina-titania.

The active metal component can include one or more metals or metalcompounds (oxides or sulfides) known in the art of hydrocracking,including those selected from the Periodic Table of the Elements IUPACGroups 6, 7, 8, 9 and 10. In certain embodiments the active metalcomponent is one or more of Mo, W, Co or Ni (oxides or sulfides). Theadditional active metal component may be contained in catalyst ineffective concentrations. For example, total active component content inhydrocracking catalysts can be present in an amount as is known in therelated art, for example about 0.01-40, 0.1-40, 1-40, 2-40, 5-40,0.01-30, 0.1-30, 1-30, 2-30, 5-30, 0.01-20, 0.1-20, 1-20, 2-20 or 5-20 W% in terms of metal, oxide or sulfide. In certain embodiments, activemetal components are loaded using a solution of oxides, and prior touse, the hydrocracking catalysts are sulfided.

In certain embodiments, a method for hydrocracking hydrocarbon oil usinga hydrocracking catalyst described herein including HOCMM as a componentcomprises introducing a hydrocarbon oil, for instance having a boilingpoint in the range of about 370-833, 370-816, 370-650, 375-833, 375-816or 375-650° C., in the presence of hydrogen, to a hydrocracking zoneincluding one or more reactors operating at a reactor temperature in therange of about 300-500, 300-450, 300-420, 350-500, 350-450 or 350-420°C., a hydrogen partial pressure in the range of about 20-100, 20-70,20-55, 30-100, 30-70, 30-55 or 40-55 bar, a liquid hourly space velocity(“LHSV”, which refers to the volumetric flow rate of the liquid feeddivided by the volume of the catalyst) in the range of about 0.1-10,0.2-1.5 h⁻¹, and a hydrogen/oil ratio of in the range of about500-2,500, 1,000-2,000 normalized cubic meters of hydrogen per cubicmeter of oil (Nm³/m³). “Hydrocracking zone” means one or more reactorsand associated effluent separation apparatus, and can contain two ormore reactors. In certain embodiments, the feed is pre-treated, or is arecycle stream, within the boiling point ranges described above, withsulfur content of less than 100 ppmw or 50 ppmw or 10 ppmw, and nitrogencontent of less than 100 ppmw or 50 ppmw or 10 ppmw.

In a method for hydrocracking hydrocarbon oil according to certainembodiments herein, the flow reactor described above can be a flowreactor selected from a stirring bath type reactor, a boiling bed typereactor, a baffle-equipped slurry bath type reactor, a fixed bed typereactor, a rotary tube type reactor and a slurry bed type reactor.

In a method for hydrocracking hydrocarbon oil according to certainembodiments herein, the hydrocarbon oil described above containspreferably heavy hydrocarbon oil obtained from (1) crude oil, (2)synthetic crude oil, (3) bitumen, (4) oil sand, (5) shale oil, (6) coalliquid (7) plastic pyrolysis oils, (8) biomass derived oils or (9)Fisher-Tropsch wax.

In a method for hydrocracking hydrocarbon oil according to certainembodiments herein, the hydrocarbon oil described above contains heavyhydrocarbon oil obtained from crude oil, synthetic crude oil, bitumen,oil sand, shell oil or coal liquid, and the above heavy hydrocarbon oilis preferably any of a) vacuum gas oil (VGO), b) deasphalted oil (DAO)obtained from a solvent deasphalting process or demetallized oil, c)light coker gas oil or heavy coker gas oil obtained from a cokerprocess, d) cycle oil obtained from a fluid catalytic cracking (FCC)process e) gas oil obtained from a visbreaking process, or f) a recyclestream obtained from hydrocracking of one or more of (a)-(e). In amethod for hydrocracking hydrocarbon oil according to certainembodiments herein, the hydrocarbon oil comprises a recycle streamobtained from hydrocracking of VGO. In a method for hydrocrackinghydrocarbon oil using a hydrocracking catalyst described hereinincluding HOCMM as a component according to certain embodiments herein,the hydrocarbon oil comprises a recycle stream obtained fromhydrocracking of VGO, straight run VGO or pre-treated straight run VGO,with selectivity to naphtha and/or middle distillates tailored as afunction of the mesophase induced in the HOCMMs described herein toallow operation flexibility. In a method for hydrocracking hydrocarbonoil using a hydrocracking catalyst described herein including HOCMM as acomponent according to certain embodiments herein, the hydrocarbon oilcomprises a recycle stream obtained from hydrocracking of VGO, straightrun VGO or pre-treated straight run VGO, with selectivity to naphthaand/or middle distillates tailored as a function of the mesophaseinduced in the HOCMMs described herein to allow operation flexibility.

In a method for hydrocracking hydrocarbon oil using a hydrocrackingcatalyst described herein including HOCMM as a component according tocertain embodiments herein, the hydrocarbon oil comprises a recyclestream obtained from hydrocracking of VGO, straight run VGO orpre-treated straight run VGO, with selectivity to naphtha and middledistillates tailored as a function of the cubic symmetry mesophaseinduced in the HOCMMs described herein to allow operation flexibility.

EXAMPLES

The HOCMMs produced in the examples herein exhibit a remarkable degreeof well-defined long-range mesoporous ordering, as given by thelow-angle XRD patterns. The parent zeolite used in the examples andcomparative examples possesses the FAU framework, zeolite Y (obtainedfrom Zeolyst International, product name CBV 720) and is referred toherein as zeolite H-Y, having a SAR of about 30. While the examples areshown with respect to this particular zeolite, the methods herein can beapplied to a parent CMM from another source and of another type asdescribed herein, whether obtained from a commercial manufacturerobtained from a separate synthesis process. Accordingly, the resultingcomposition of matter has the mesoporous structure with microporosityand CMM structure corresponding to the parent CMM.

Characterizations herein were carried out as follows. Powder x-raydiffraction patterns were obtained using a Bruker D8 twindiffractometer, operating at 40 kV and 40 mA having Cu Kα radiation(λ=0.154 nm) and a step-size of 0.02°. N₂ physisorption measurementswere conducted at 77 K using a Micromeritics ASAP 2420 instrument. Allsamples were degassed at 350° C. for 12 h before the analysis. Thespecific surface areas and pore size distributions were calculated usingthe Brunauer-Emmett-Teller (BET) and non-local density functional theory(NLDFT) models. The t-plot method was used to calculate the microporevolume. High-resolution transmission electron microscopy (TEM) studieswere undertaken using a FEI-Titan ST electron microscope operated at 300kV.

Example 1A: A quantity of 1.2 grams of urea was dissolved in 60.0 g ofwater to form a homogeneous solution. To this mixture, 2.0 g of zeoliteH-Y was added and stirred for 10 minutes. Subsequently, 3.0 millilitersof an organosilane, dimethyloctadecyl(3-trimethoxysilyl-propyl)-ammoniumchloride (42.0 wt % in methanol), was added. The resulting solution wasstirred for 0.5 hours, followed by hydrothermal treatment at 130° C. for72 hours. The resulting mixture was filtered, washed with water anddried at 120° C. for 24 hours. The synthesized product was calcined inair at 550° C. for 6 hours with a ramp rate of 60° C./hour to yieldY-U-TMS (in which Y refers to zeolite Y, U refers to urea and TMS refersto dimethyloctadecyl(3-trimethoxysilyl-propyl)-ammonium chloride).

Example 1B: A procedure for synthesis of 3D-cubic ordered mesoporousFAU-type zeolites is provided. A quantity of 1.2 grams of urea wasdissolved in 60.0 g of water to form a homogeneous solution. To thismixture, 0.2 g of ammonium nitrate (NH₄NO₃) was added as a source ofionic co-solute, and stirred to form a homogeneous solution. 2.0 g ofzeolite H-Y was added and stirred for 10 minutes. Subsequently, 3.0milliliters of an organosilane,dimethyloctadecyl(3-trimethoxysilyl-propyl)-ammonium chloride (42.0 wt %in methanol), was added. The resulting solution was stirred for 0.5hours, followed by hydrothermal treatment at 130° C. for 72 hours. Theresulting solids were filtered, washed with water and dried at 120° C.for 24 hours. The synthesized product was calcined in air at 550° C. for6 hours with a ramp rate of 60° C./hour to yield Y-U-N-TMS (in which Yrefers to zeolite Y, N refers to nitrate, U refers to urea and TMSrefers to dimethyloctadecyl(3-trimethoxysilyl-propyl)-ammoniumchloride). Structural and textural properties of Y-U-N-TMS are providedin Table 3.

When comparing the Examples 1A and 1B, the benefit of the ionicco-solute contribution of the nitrate is apparent. The ionic co-soluteserves to influence the cubic micelle shape by the Hofmeister effect,around with the FAU-type zeolite oligomers are arranged. FIG. 3A depictslow-angle XRD patterns, FIG. 3B depicts high-angle XRD patterns, FIG. 4Adepicts N₂ physisorption isotherms and FIG. 4B depicts DFT pore-sizedistributions, wherein “a” corresponds to commercial-USY (Zeolite H-Y),“b” corresponds to Y-U-TMS, and “c” corresponds to Y-U-N-TMS: In theExample 1A there is a degree of periodicity of mesopore arrangementpossibly from either a bimodal system or a structure collapse, however,there is a significant lack of any long-range ordering as compared withthe Example 1B having the nitrate anion where, in FIG. 3A, it isobserved by low angle XRD showing reflections characteristic of gyrodialbicontinuous (cubic) mesopore structure (Ia-3d). In the Example 1B, theproduct hierarchically ordered zeolite is a 3D-cubic ordered mesoporousFAU-type zeolite, having cubic mesoporous channels present in the [100]and [110] directions with FAU micropore channels in the walls and massof the mesostructure between mesopores. FIGS. 5A-B are TEM micrographsof Y-U-N-TMS showing cubic mesoporous channels in the [111] and [110]directions with FAU micropore channels in the walls of themesostructure, wherein: FIG. 5A shows the TEM micrograph at a scale of100 nanometers; FIG. 5B shows the TEM micrograph in the [110] directionand in the [111] direction at a scale of 20 nanometers. In addition,FIG. 5C depicts a FAU unit cell schematic and dimensions and theirarrangement to provide long-range mesoporous ordering. The high-degreeof long-range ordering is apparent from FIG. 3A, where low-angle XRDpatterns exhibit Bragg's reflections 211, 220, 321, 400, 420 and 332,which are characteristic of bicontinuous gyroid (cubic) (Ia-3d) mesoporesymmetry (where the reflections at 321, 400, 420 and 332 are show at 8times magnification)I. The retention of the underlying zeolite structureis apparent from FIG. 3B, where high-angle XRD patterns are consistentwith those for the parent zeolite, FAU zeolite. FIGS. 4A and 4B depictthe N₂ physisorption isotherms and pore-size distributions of preparedzeolites. Y-U-N-TMS has shown excellent hierarchically orderedmesoporosity as indicated by characteristic type-IV isotherm with H1hysteresis. In addition, a high mesopore volume and narrow pore-sizedistribution further supports the presence of long-range orderedmesoporosity.

According to the examples herein, a hierarchically ordered FAU-typeframework exhibiting 3D-cubic (Ia-3d) mesopore symmetry is prepared forthe first time by a methodical post-synthetic reassembly.

Example 2: The catalytic properties of the Y-U-N-TMS 3D-cubic orderedmesoporous FAU-type zeolite were evaluated for the low-pressurehydrocracking of a recycle stream (2nd stage feedstock) from a two-stagehydrocracking unit using a fixed-bed reactor. The feedstock is apretreated straight-run vacuum gas oil from a first stage hydrocrackingunit, and therefore contains very low levels of sulfur and nitrogen, 40ppmw and 17 ppmw, respectively. The composition and properties of thefeedstock are tabulated in Table 4. The catalysts were prepared bymixing the mesoporous FAU-type zeolite (30 wt %) with alumina (70 wt %),followed by incipient wet-impregnation of nickel (Ni) and molybdenum(Mo) species. In particular, 70 wt % alumina was dispersed in a minimumamount of deionized (DI) water. To this slurry, 30 wt % zeolite wasadded slowly and stirred for 15 min. In the next step, the desiredamounts of (NH₄)₆Mo₇O₂₄·4H₂O (8.5 wt % Mo), Ni(NO₃)₂·6H₂O (3.0 wt % Ni)and citric acid (7.5 wt %) were added to the slurry of zeolite-aluminaand stirred for another 1 h. The thus obtained mixture was dried at 120°C. overnight, followed by calcination at 550° C. for 4 h. The obtainedmetal oxide loaded catalysts in powder form were sulfided in a batchreactor (Parr) at 300° C. and 50 bars for 4 h using dimethyldisulfide (1mL g⁻¹ of catalyst) as a sulfiding agent in the presence of hydrogen at40 bars. The catalyst bed was prepared by packing 0.5 g of sulfidecatalyst between two silicon carbide (46 mesh) layers each (16 ml involume) in a stainless steel cylindrical reactor (SS316; internaldiameter-9.1 mm; length-300 mm) with a 20 μm porous plate located at thebottom. The loaded catalyst was purged with a H₂/N₂ (75:25 volume ratio)gas mixture at a flow rate of 100 ml/h at 450° C. and 50 bars for 2 h toremove any moisture. The catalytic studies were performed at 400° C.temperature and 50 bars pressure with the H₂/oil ratio of 750 Nm³/m³ andweight hour space velocity (WHSV) of 1 h⁻¹. The reaction was performedfor 10 h, and the liquids were separated from the liquid-gas separatorand collected periodically after every hour for gas chromatography (GC)analysis. The liquid products were analyzed according to the ASTM D2887standard test method using Agilent 6980N GC coupled with simulateddistillation (SIMDIS) software.

Conversion (X) of the feed, selectivity (S) and yield (Y) to the desiredhydrocarbon mixtures were calculated according to equations (1), (2) and(3), respectively:

$\begin{matrix}{X = {\left( \frac{R.W._{Feed}^{{370} +}{- {R.W._{Product}^{{370} +}}}}{R.W._{Feed}^{{370} +}} \right) \times 100}} & (1)\end{matrix}$

where R.W._(Feed) ³⁷⁰⁺ and R.W._(Product) ³⁷⁰⁺ correspond to theremaining fraction of material (wt. %) in the feed and product at aboiling point ≥370° C.

$\begin{matrix}{S_{x - y} = {\left( \frac{R.W._{Product}^{x - y}{- {R.W._{Feed}^{x - y}}}}{R.W._{Feed}^{{370} +}{- {R.W._{Product}^{{370} +}}}} \right) \times 100}} & (2)\end{matrix}$ $\begin{matrix}{Y_{x - y} = {\left( \frac{R.W._{Product}^{x - y}{- {R.W._{Feed}^{x - y}}}}{R.W._{Feed}^{{370} +}} \right) \times 100}} & (3)\end{matrix}$

where R.W._(Product) ^(x-y) and R.W._(Feed) ^(x-y) correspond to thefraction of material (wt. %) in the product and the feed between theboiling points ‘x and y’. S_(x-y) and Y_(x-y) correspond to selectivityand yield of the hydrocarbon fractions between boiling points ‘x and y’.

Table 5 shows acid properties of the parent zeolite and the synthesizedY-U-N-TMS, and catalytic performance. Despite having a lowerconcentration of zeolitic acid sites compared with the parent zeolite,the HOCMM synthesized herein demonstrates excellent catalyticperformance. FIG. 6 is a plot of hydrocracking activity (conversionpercentage per acid site) and selectivity (naphtha, middle distillatesand heavy distillates) of the parent zeolite and the synthesizedY-U-N-TMS. The HOCMM synthesized herein demonstrates higher conversionand naphtha selectivity compared with the parent zeolite.

Tailoring of the mesophase symmetry, and the associated physicochemicalproperties that are induced by realizing cubic symmetry mesophase,resulted in increased product selectivity, namely higher naphtha andmiddle distillate yields.

The improved naphtha selectivity indicates improved accessibility toacid sites, secondary cracking of middle-distillate hydrocarbons tonaphtha hydrocarbons likely occurs. The synthesized Y-U-N-TMS possess ahigh B/L acid site ratio and 3D-mesostructure, demonstrates excellentconversion of the VGO feedstock, and good selectivity to naphtha andmiddle distillates.

As used herein, the phrase “a major portion” with respect to aparticular composition and/or solution and/or other parameter means atleast about 50% and up to 100% of a unit or quantity. As used herein,the phrase “a significant portion” with respect to a particularcomposition and/or solution and/or other parameter means at least about75% and up to 100% of a unit or quantity. As used herein, the phrase “asubstantial portion” with respect to a particular composition and/orsolution and/or other parameter means at least about 90, 95, 98 or 99%and up to 100% of a unit or quantity. As used herein, the phrase “aminor portion” with respect to a particular composition and/or solutionand/or other parameter means at least about 1, 2, 4 or 10%, up to about20, 30, 40 or 50% of a unit or quantity.

It is to be understood that like numerals in the drawings represent likeelements through the several figures, and that not all components and/orsteps described and illustrated with reference to the figures arerequired for all embodiments or arrangements. Further, the terminologyused herein is for the purpose of describing particular embodiments onlyand is not intended to be limiting of the invention. As used herein, thesingular forms “a”, “an” and “the” are intended to include the pluralforms as well, unless the context clearly indicates otherwise. It willbe further understood that the terms “including,” “comprising,”“having,” “containing,” “involving,” and variations thereof herein, whenused in this specification, specify the presence of stated features,integers, steps, operations, elements, and/or components, but do notpreclude the presence or addition of one or more other features,integers, steps, operations, elements, components, and/or groupsthereof.

It should be noted that use of ordinal terms such as “first,” “second,”“third,” etc., in the claims to modify a claim element does not byitself connote any priority, precedence, or order of one claim elementover another or the temporal order in which acts of a method areperformed, but are used merely as labels to distinguish one claimelement having a certain name from another element having a same name(but for use of the ordinal term) to distinguish the claim elements.

Notably, the figures and examples above are not meant to limit the scopeof the present disclosure to a single implementation, as otherimplementations are possible by way of interchange of some or all thedescribed or illustrated elements. Moreover, where certain elements ofthe present disclosure can be partially or fully implemented using knowncomponents, only those portions of such known components that arenecessary for an understanding of the present disclosure are described,and detailed descriptions of other portions of such known components areomitted so as not to obscure the disclosure. In the presentspecification, an implementation showing a singular component should notnecessarily be limited to other implementations including a plurality ofthe same component, and vice-versa, unless explicitly stated otherwiseherein. Moreover, applicants do not intend for any term in thespecification or claims to be ascribed an uncommon or special meaningunless explicitly set forth as such. Further, the present disclosureencompasses present and future known equivalents to the known componentsreferred to herein by way of illustration.

The foregoing description of the specific implementations will so fullyreveal the general nature of the disclosure that others can, by applyingknowledge within the skill of the relevant art(s), readily modify and/oradapt for various applications such specific implementations, withoutundue experimentation, without departing from the general concept of thepresent disclosure. Such adaptations and modifications are thereforeintended to be within the meaning and range of equivalents of thedisclosed implementations, based on the teaching and guidance presentedherein. It is to be understood that the phraseology or terminologyherein is for the purpose of description and not of limitation, suchthat the terminology or phraseology of the present specification is tobe interpreted by the skilled artisan in light of the teachings andguidance presented herein, in combination with the knowledge of oneskilled in the relevant art(s). It is to be understood that dimensionsdiscussed or shown are drawings accordingly to one example and otherdimensions can be used without departing from the disclosure.

The subject matter described above is provided by way of illustrationonly and should not be construed as limiting. Various modifications andchanges can be made to the subject matter described herein withoutfollowing the example embodiments and applications illustrated anddescribed, and without departing from the true spirit and scope of theinvention encompassed by the present disclosure, which is defined by theset of recitations in the following claims and by structures andfunctions or steps which are equivalent to these recitations.

TABLE 1 Crystal systems. System Unit cell Essential symmetry of crystalTriclinic No special relationship None Monoclinic a ≠ b ≠ c Two-foldaxis or mirror plane α = γ = 90° ≠ β (inverse two-fold axis)Orthorhombic a ≠ b ≠ c Three orthogonal two-fold or α = β = γ = 90°inverse two-fold axes Tetragonal a = b ≠ c One four-fold or inversefour- α = β = γ = 90° fold axis Trigonal a = b = c One three-fold axisor inverse α = β = γ ≠ 90° three-fold axis Hexagonal a = b ≠ c Onesix-fold or inverse six- α = β = 90°, γ = 120° fold axis Cubic a = b = cFour three-fold axes

TABLE 2 Crystal classes Crystal classes (point group) Non- Systemcentrosymmetric Centrosymmetric Triclinic 1 1 Monoclinic 2, m (=2) 2/mOrthorhombic 222, 2 mm mmm Tetragonal 4, 4 4/m 422, 4 mm, 42 m    4/mmmTrigonal 3 3 32, 3 m 3 m Hexagonal 6, 6 6/m 622, 6 mm, 62 m    6/mmmCubic 23 m3 432, 43 m m3m

TABLE 3 Structural and textural properties of hierarchical zeolites a₀(nm) ^(a) S_(BET) (m² g⁻¹) ^(c) V_(p) (cm³ g⁻¹) ^(e) Sample micro^(§)meso^(¶) Si/Al ^(b) Micro Total D (nm) ^(d) Micro Total Y-U-N-TMS 24.3610.1^(¢) 11.1 436 853 4.2 0.18 0.51 HY-30 24.28 — 14.8 561 820 — 0.270.31 Y-U-TMS 24.21 — 13.9 417 804 — 0.16 0.39 ^(a) Unit-cell parameter;^(b) from ²⁹Si magic angle spinning-NMR; ^(c) Brunauer-Emmett-Teller(BET) surface area; ^(d) mesopore size; ^(e) pore volume; ^(§)calculatedfrom calcined high-angle x-ray diffraction (XRD) patterns;^(¶)calculated from calcined low-angle (LA) XRD patterns usingformula-^(¢)a = d√(h² + k² + l²).

TABLE 4 Composition and properties of feedstock Density at 15° C., g/cm³0.8391 Sulfur, ppmw 40 Nitrogen, ppmw 17 Initial boiling point, ° C. 2915/10 wt %, ° C. 353/374 30/50 wt %, ° C. 414/441 70/90 wt %, ° C.467/503 95 wt %, ° C. 521 Final boiling point, ° C. 568

TABLE 5 Acid properties and catalytic activities* Y (%)^(£) X_(VGO) Mid.Gas Zeolite BAS^(§) LAS^(¥) Total B/L^(¶) (%)^(¢) Naphtha Dist. oilY-U-N- 127.6  77.1 204.7 1.7 54.6 30.6 15.3  6.7 TMS HY-30 275.6 443.1718.7 0.6 46.8 22.8 12.8 11.1 *from pyridine FT-IR recorded at 150° C.;^(§)Brønsted acid sites; ^(¥)Lewis acid sites; ^(¶)Brønsted/Lewis acidratio; ^(¢)Conversion; ^(£)Yield. Acidity units are micro-moles ofadsorbate per gram of zeolite (μmol_(NH3)/g).

1. A composition of matter comprising hierarchically ordered crystallinemicroporous material having well-defined long-range mesoporous orderingof cubic symmetry comprising mesopores having walls of crystallinemicroporous material and a mass of mesostructure between mesopores ofcrystalline microporous material, wherein the long-range ordering isdefined by presence of secondary peaks in an X-ray diffraction (XRD)pattern and/or cubic symmetry observable by microscopy.
 2. A compositionof matter comprising hierarchically ordered crystalline microporousmaterial having well-defined long-range mesoporous ordering of cubicsymmetry comprising mesopores having walls of crystalline microporousmaterial and a mass of mesostructure between mesopores of crystallinemicroporous material, wherein at least a portion of the mesoporescontain micelles of supramolecular templates shaped to induce mesoporousordering of cubic symmetry, and wherein the supramolecular templatespossess one or more dimensions larger than dimensions of micropores ofthe crystalline microporous material to constrain diffusion intomicropores of the crystalline microporous material, wherein thedimensions relate to a head group of a supramolecular template, a tailgroup of a supramolecular template, or a co-template arrangement thatconstrain diffusion into micropores of the crystalline microporousmaterial.
 3. The composition of matter as in claim 2, further comprisingan ionic co-solute.
 4. The composition of matter as claim 3, wherein theionic co-solute comprises NO₃ ⁻.
 5. The composition of matter as inclaim 1, wherein the cubic mesophase possess Ia-3d, Fm-3m, Pm-3n, Pn-3mor Tm-3m symmetry.
 6. The composition of matter as in claim 1, whereinthe cubic mesophase possess Ia-3d symmetry and secondary peaks in XRDare present at one or more of (220), (321), (400), (420) or (332)reflections.
 7. The composition of matter as in claim 1, wherein thecubic mesophase possess Ia-3d symmetry and long-range ordering isobservable by microscopy viewing an electron beam down a [311], [111] or[110] zone axis, or wherein the cubic mesophase possess Fm-3m symmetryand long-range ordering is observable by microscopy viewing an electronbeam down a [001] or [110] zone axis.
 8. (canceled)
 9. The compositionof matter as in claim 1, wherein said crystalline microporous materialcomprises a zeolite or zeolite-type material.
 10. The composition ofmatter as in claim 1, wherein said crystalline microporous material is azeolite having a framework selected from the group consisting of AEI,*BEA, CHA, FAU, MFI, MOR, LTL, LTA and MWW.
 11. The composition ofmatter as in claim 1, wherein said parent crystalline microporousmaterial is a zeolite having FAU framework.
 12. A hydrocracking catalystcomprising the hierarchically ordered crystalline microporous materialas in claim 9, an inorganic oxide component as a binder, and an activemetal component, wherein the hierarchically ordered crystallinemicroporous material comprises about 0.1-99 wt % of the hydrocrackingcatalyst.
 13. (canceled)
 14. The hydrocracking catalyst as in claim 12,wherein the inorganic oxide component is selected from the groupconsisting of alumina, silica, titania, silica-alumina, alumina-titania,alumina-zirconia, alumina-boria, phosphorus-alumina,silica-alumina-boria, phosphorus-alumina-boria,phosphorus-alumina-silica, silica-alumina-titania,silica-alumina-zirconia, alumina-zirconia-titania,phosphorous-alumina-zirconia, alumina-zirconia-titania andphosphorus-alumina-titania.
 15. The hydrocracking catalyst as in claim12, wherein the inorganic oxide component comprises alumina.
 16. Thehydrocracking catalyst as in claim 15, wherein the crystallinemicroporous material comprises FAU zeolite.
 17. The hydrocrackingcatalyst as in claim 16, wherein the active metal component comprisesone or more of Mo, W, Co or Ni (oxides or sulfides).
 18. Thehydrocracking catalyst as in claim 12, wherein the active metalcomponent comprises one or more metals selected from the Periodic Tableof the Elements IUPAC Groups 6, 7, 8, 9 or
 10. 19. A method forhydrocracking hydrocarbon oil, comprising: hydrocracking hydrocarbon oilwith a hydrocracking catalyst as claim
 18. 20. (canceled)
 21. Thecomposition of matter as in claim 2, wherein said crystallinemicroporous material comprises a zeolite or zeolite-type material. 22.The composition of matter as in claim 2, wherein said crystallinemicroporous material is a zeolite having a framework selected from thegroup consisting of AEI, *BEA, CHA, FAU, MFI, MOR, LTL, LTA and MWW. 23.The composition of matter as in claim 2, wherein said parent crystallinemicroporous material is a zeolite having FAU framework.